Herbicidal compositions

ABSTRACT

Herbicides containing compositions of glycolic acid amides and other active ingredients.

This application is a division of application Ser. No. 627,965, filed Nov. 3, 1975, now U.S. Pat. No. 4,057,414, issued Nov. 8, 1977.

The present invention application relates to herbicides containing compositions of sulfonylglycolic acid amides or sulfonylglycolic acid imides.

It is known that pyridazones (German Pat. No. 1,105,232), benzofuranyl sulfonates (German Laid-Open Application DOS 1,926,139), benzofuranylalkylamino sulfonates (German Laid-Open Application DOS 2,324,592), azetidine carbothiolates (German Laid-Open Application DOS 2,312,045), fatty acids (German Pat. No. 959,066), thiol carbamates (U.S. Pat. Nos. 3,185,720 and 3,330,821), carbamates (German Laid-Open Application DOS 1,567,151; German Printed Application DAS 1,137,255), pyrazolium compounds (German Laid-Open Application DOS 2,260,485), α-cyanoacrylates (German Laid-Open Application DOS 1,642,231), anilides (British Pat. No. 903,766) and 1,2,4-triazinones (German Laid-Open Application DOS 2,138,031) have a herbicidal action. However, this action is not always satisfactory.

We have now found that compositions of one or more of these active ingredients and sulfonylglycolic acid amides (German Laid-Open Applications DOS 2,201,432 and 2,334,715) or sulfonylglycolic acid imides (German Laid-Open Application DOS 2,219,923), which are known as individual herbicidal active ingredients, have an unforeseeably superior herbicidal action over their individual components.

These compositions consist of

(a) a glycolic acid amide of the formula ##STR1## R¹ denoting alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl of a maximum of 6 carbon atoms, alkoxyalkyl, haloalkoxyalkyl, alkenoxyalkyl, alkynoxyalkyl or cycloalkyl, and R² denoting phenyl which may bear one or more identical or different substituents, the number of substituents, which may be halogen, lower alkyl of a maximum of 4 carbon atoms, haloalkyl, alkoxy, alkylsulfonyl, alkylaminosulfonyl, cyano, hydroxy, nitro or amino, being from 0 to 3, and the carbonamide nitrogen being a ring member of an optionally bicyclic cycloalkylimine which may be substituted by halogen or lower alkyl; which may contain further hetero atoms in the ring; and which has a maximum of 9 carbon atoms, and Y denotes ##STR2## R³, R⁴, R⁵ and R⁶ denoting alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl of a maximum of 8 carbon atoms, unsubstituted or substituted phenyl or cycloalkyl of a maximum of 8 carbon atoms, and R⁴ and R⁵ additionally denoting hydrogen, and

(b) a phenyl carbamate of the formula ##STR3## where Y denotes hydrogen or methyl, R denotes methoxy, ethoxy, ##STR4## X denotes identical or different substituents such as halogen, haloalkyl, lower alkyl or methoxy, and n denotes one of the integers 0, 1, 2 and 3.

Examples of suitable components for compositions according to the invention are the active ingredients listed below:

    ______________________________________                                          ##STR5##                                                                      R.sup.1          R.sup.2                                                       ______________________________________                                         CH.sub.3         H                                                             CH.sub.3         CH.sub.3                                                      CH.sub.3         C.sub.2 H.sub.5                                               CH.sub.3         CH.sub.2 CH.sub.2 Cl                                          CH.sub.3         n-C.sub.3 H.sub.7                                             CH.sub.3         i-C.sub.3 H.sub.7                                             CH.sub.3         n-C.sub.4 H.sub.9                                             CH.sub.3         sec-C.sub.4 H.sub.9                                           CH.sub.3         i-C.sub.4 H.sub.9                                             CH.sub.3                                                                                         ##STR6##                                                     CH.sub.3                                                                                         ##STR7##                                                     CH.sub.3                                                                                         ##STR8##                                                     C.sub.2 H.sub.5  CH.sub.3                                                      C.sub.2 H.sub.5  C.sub.2 H.sub.5                                               C.sub.2 H.sub.5  CH.sub.2 CH.sub.2 Cl                                          C.sub.2 H.sub.5  n-C.sub.3 H.sub.7                                             C.sub.2 H.sub.5  i-C.sub.3 H.sub.7                                             n-C.sub.3 H.sub.7                                                                               CH.sub.3                                                      n-C.sub.3 H.sub.7                                                                               i-C.sub.3 H.sub.7                                             C.sub.2 H.sub.5  H                                                             i-C.sub.3 H.sub.7                                                                               H                                                             i-C.sub.3 H.sub.7                                                                               CH.sub.3                                                      i-C.sub.3 H.sub.7                                                                               C.sub.2 H.sub.5                                               i-C.sub.3 H.sub.7                                                                               CH.sub.2 CH.sub.2 Cl                                          i-C.sub.3 H.sub.7                                                                               n-C.sub.3 H.sub.7                                             i-C.sub.3 H.sub.7                                                                               i-C.sub.3 H.sub.7                                             i-C.sub.3 H.sub.7                                                                               n-C.sub.4 H.sub.9                                             i-C.sub.3 H.sub.7                                                                               sec-C.sub.4 H.sub.9                                           i-C.sub.3 H.sub.7                                                                                ##STR9##                                                     CH.sub.2CHCH.sub.2                                                                              CH.sub.3                                                      CH.sub.2CCH      CH.sub.3                                                      CH.sub.2CCH      i-C.sub.3 H.sub.7                                             n-C.sub.4 H.sub.9                                                                               CH.sub.3                                                      n-C.sub.4 H.sub.9                                                                               C.sub.2 H.sub.5                                               n-C.sub.4 H.sub.9                                                                               n-C.sub.3 H.sub.7                                             n-C.sub.4 H.sub.9                                                                               i-C.sub.3 H.sub.7                                             sec.-C.sub.4 H.sub.9                                                                            H                                                             sec.-C.sub.4 H.sub.9                                                                            CH.sub.3                                                      sec.-C.sub.4 H.sub.9                                                                            C.sub.2 H.sub.5                                               sec.-C.sub.4 H.sub.9                                                                            CH.sub.2 CH.sub.2 Cl                                          sec.-C.sub.4 H.sub.9                                                                            n-C.sub.3 H.sub.7                                             sec.-C.sub.4 H.sub.9                                                                            i-C.sub.3 H.sub.7                                             i-C.sub.4 H.sub.9                                                                               i-C.sub.3 H.sub.7                                             tert.-C.sub.4 H.sub.9                                                                           CH.sub.3                                                      tert.-C.sub.4 H.sub. 9                                                                          C.sub.2 H.sub.5                                               tert.-C.sub.4 H.sub.9                                                                           CH.sub.2 CH.sub.2 Cl                                          tert.-C.sub.4 H.sub.9                                                                           i-C.sub.3 H.sub.7                                              ##STR10##       H                                                              ##STR11##       CH.sub.3                                                       ##STR12##       C.sub.2 H.sub.5                                                ##STR13##       CH.sub.2 CH.sub.2 Cl                                           ##STR14##       n-C.sub.3 H.sub.7                                              ##STR15##       i-C.sub.3 H.sub.7                                              ##STR16##       n-C.sub.4 H.sub.9                                              ##STR17##       i-C.sub.3 H.sub.7                                             ______________________________________                                          ##STR18##                                                                     R.sup.1         R.sup.2       R.sup.3                                          ______________________________________                                          ##STR19##      CH.sub.3      CH.sub.3                                          ##STR20##      CH.sub.3      CH.sub.3                                          ##STR21##      CH.sub.3      CH.sub.3                                          ##STR22##      CH.sub.3      CH.sub.3                                          ##STR23##      CH.sub.3      C.sub.2 H.sub.5                                   ##STR24##      CH.sub.3      C.sub.2 H.sub.5                                   ##STR25##      CH.sub.3      C.sub.2 H.sub.5                                   ##STR26##      CH.sub.3      C.sub.2 H.sub.5                                   ##STR27##      CH.sub.3      i-C.sub.3 H.sub.7                                 ##STR28##      CH.sub.3      i-C.sub.3 H.sub.7                                 ##STR29##      CH.sub.3      i-C.sub.3 H.sub.7                                 ##STR30##      CH.sub.3      i-C.sub.3 H.sub.7                                 ##STR31##      CH.sub.3      i-C.sub.3 H.sub.7                                 ##STR32##      C.sub.2 H.sub.5                                                                              CH.sub.3                                          ##STR33##      C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                   ##STR34##      C.sub.2 H.sub.5                                                                              n-C.sub.3 H.sub.7                                 ##STR35##      C.sub.2 H.sub.5                                                                              i-C.sub.3 H.sub.7                                 ##STR36##      C.sub.2 H.sub.5                                                                              i-C.sub.3 H.sub.7                                 ##STR37##      i-C.sub.3 H.sub.7                                                                            CH.sub.3                                          ##STR38##      i-C.sub.3 H.sub.7                                                                            CH.sub.3                                          ##STR39##      i-C.sub.3 H.sub.7                                                                            C.sub.2 H.sub.5                                   ##STR40##      i-C.sub.3 H.sub.7                                                                            n-C.sub.3 H.sub.7                                 ##STR41##      i-C.sub.3 H.sub.7                                                                            i-C.sub.3 H.sub.7                                 ##STR42##      i-C.sub.3 H.sub.7                                                                            i-C.sub.3 H.sub.7                                 ##STR43##                                                                                      ##STR44##    i-C.sub.3 H.sub.7                                ______________________________________                                          ##STR45##                                                                     R.sup.3      R.sup.1     R.sup.2                                               ______________________________________                                         CH.sub.3     CH.sub.3    CH.sub.3                                              CH.sub.3     CH.sub.3    C.sub.2 H.sub.5                                       C.sub.2 H.sub.5                                                                             CH.sub.3    CH.sub.3                                              C.sub.2 H.sub.5                                                                             CH.sub.3    C.sub.2 H.sub.5                                       i-C.sub.3 H.sub.7                                                                           CH.sub.3    CH.sub.3                                              i-C.sub.3 H.sub.7                                                                           CH.sub.3    C.sub.2 H.sub.5                                       i-C.sub.3 H.sub.7                                                                           C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                       i-C.sub.3 H.sub.7                                                                           CH.sub.3    CH.sub.2 CH.sub.2 Cl                                  sec.-C.sub.4 H.sub.9                                                                        CH.sub.3    CH.sub.3                                              ______________________________________                                          ##STR46##                                                                      R.sup.1         R.sup.2                                                       ______________________________________                                         CH.sub.2CCH      CH.sub.3                                                      i-C.sub.3 H.sub.7                                                                               C.sub.2 H.sub.5                                               i-C.sub.3 H.sub.7                                                                               n-C.sub.3 H.sub.7                                             i-C.sub.3 H.sub.7                                                                               i-C.sub.3 H.sub.7                                             i-C.sub.3 H.sub.7                                                                               n-C.sub.4 H.sub.9                                             tert.-C.sub.4 H.sub.9                                                                           CH.sub.3                                                      sec.-C.sub.4 H.sub.9                                                                            CH.sub.3                                                      i-C.sub.4 H.sub.9                                                                               CH.sub.3                                                       ##STR47##       CH.sub.3                                                       ##STR48##       CH.sub.3                                                       ##STR49##       C.sub.2 H.sub.5                                                ##STR50##       n-C.sub.3 H.sub.7                                              ##STR51##       i-C.sub.3 H.sub.7                                              ##STR52##       n-C.sub.4 H.sub.9                                              ##STR53##                                                                                       ##STR54##                                                     ##STR55##                                                                                       ##STR56##                                                    i-C.sub.3 H.sub.7                                                                               CH.sub.3                                                       ##STR57##       CH.sub.3                                                      ______________________________________                                          ##STR58##                                                                     R.sup.1   R.sup.2           R.sup.3                                            ______________________________________                                          ##STR59##                                                                               CH.sub.2OCH.sub.3 CH.sub.3                                            ##STR60##                                                                               CH.sub.2OCH.sub.3 CH.sub.3                                            ##STR61##                                                                               CH.sub.2OCH.sub.3 CH.sub.3                                            ##STR62##                                                                               CH.sub.2OCH.sub.3 CH.sub.2 Cl                                         ##STR63##                                                                               CH.sub.2OCH.sub.3 C.sub.2 H.sub.5                                     ##STR64##                                                                               CH.sub.2OCH.sub.3 i-C.sub.3 H.sub.7                                   ##STR65##                                                                               CH.sub.2OCH.sub.3 CH.sub.3                                            ##STR66##                                                                               CH.sub.2OCH.sub.3 C.sub.2 H.sub.5                                     ##STR67##                                                                               CH.sub.2OC.sub.2 H.sub.5                                                                         CH.sub.3                                            ##STR68##                                                                               CH.sub.2OC.sub.2 H.sub.5                                                                         CH.sub.3                                            ##STR69##                                                                               CH.sub.2OC.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                     ##STR70##                                                                               CH.sub.2OC.sub.2 H.sub.5                                                                         i-C.sub.3 H.sub.7                                   ##STR71##                                                                               CH.sub.2OC.sub.2 H.sub.5                                                                         CH.sub.3                                            ##STR72##                                                                               CH.sub.2 OC.sub.2 H.sub.5                                                                        CH.sub.2CH(CH.sub.3).sub.2                          ##STR73##                                                                               CH.sub.2OC.sub.3 H.sub.7 n                                                                       CH.sub.3                                            ##STR74##                                                                               CH.sub.2OC.sub.3 H.sub.7 n                                                                       C.sub.2 H.sub.5                                     ##STR75##                                                                               CH.sub.2OCH(CH.sub.3).sub.2                                                                      C.sub.2 H.sub.5                                     ##STR76##                                                                                ##STR77##        C.sub.2 H.sub.5                                     ##STR78##                                                                               CH.sub.2OCH(CH.sub.3).sub.2                                                                      CH.sub.3                                            ##STR79##                                                                                ##STR80##        CH.sub.3                                            ##STR81##                                                                               CH.sub.2OC.sub.3 H.sub.7 n                                                                       CH.sub.3                                            ##STR82##                                                                               CH.sub.2OCH(CH.sub.3).sub.2                                                                      CH.sub.3                                            ##STR83##                                                                               CH.sub.2OC.sub.3 H.sub.7 n                                                                       CH.sub.3                                            ##STR84##                                                                               CH.sub.2OCH.sub.2CHCH.sub.2                                                                      CH.sub.3                                            ##STR85##                                                                               CH.sub.2OCH.sub.2CCH                                                                             CH.sub.3                                            ##STR86##                                                                               CH.sub.2OCH(CH.sub.3).sub.2                                                                      CH.sub.3                                            ##STR87##                                                                               CH.sub.2OCH(CH.sub.3)C.sub.2 H.sub.5                                                             CH.sub.3                                            ##STR88##                                                                               CH.sub.2OC(CH.sub.3).sub.3                                                                       CH.sub.3                                            ##STR89##                                                                               CH.sub.2OCH(CH.sub.3)C.sub.2 H.sub.5                                                             C.sub.2 H.sub.5                                     ##STR90##                                                                               CH.sub.2OCH.sub.2CHCH.sub.2                                                                      CH.sub.3                                            ##STR91##                                                                               CH.sub.2OCH.sub.2CH(CH.sub.3).sub.2                                                              CH.sub.3                                           ______________________________________                                          ##STR92##                                                                     R                   n                                                          ______________________________________                                         CH.sub.3            4                                                          C.sub. 2 H.sub.5    4                                                          CH.sub.2 CH.sub.2 Cl                                                                               4                                                          i-C.sub.3 H.sub.7   4                                                          n-C.sub.3 H.sub.7   4                                                          n-C.sub.4 H.sub.9   4                                                          sec.-C.sub.4 H.sub.9                                                                               4                                                          i-C.sub.4 H.sub.9   4                                                          CH.sub.3            5                                                          C.sub.2 H.sub.5     5                                                          n-C.sub.3 H.sub.7   5                                                          i-C.sub.3 H.sub.7   5                                                          n-C.sub.4 H.sub.9   5                                                          CH.sub.3            6                                                          C.sub.2 H.sub.5     6                                                          CH.sub.2 CH.sub.2 Cl                                                                               6                                                          n-C.sub.3 H.sub.7   6                                                          i-C.sub.3 H.sub.7   6                                                          n-C.sub.4 H.sub.9   6                                                          sec.-C.sub.4 H.sub.9                                                                               6                                                          CH(C.sub.2 H.sub.5).sub.2                                                                          6                                                          CH.sub.2CH(CH.sub.3)C.sub.2 H.sub.5                                                                6                                                          CH.sub.3            7                                                          C.sub.2 H.sub.5     7                                                          i-C.sub.3 H.sub.7   7                                                          n-C.sub.3 H.sub.7   7                                                          CH.sub.2CH.sub.2Cl  7                                                          H                   8 (bicyclo)                                                CH.sub.3            8 (bicyclo)                                                C.sub.2 H.sub.5     8 (bicyclo)                                                i-C.sub.3 H.sub.7   8 (bicyclo)                                                n-C.sub.3 H.sub.7   8 (bicyclo)                                                n-C.sub.4 H.sub.9   8 (bicyclo)                                                sec.-C.sub.4 H.sub.9                                                                               8 (bicyclo)                                                i-C.sub.4 H.sub.9   8 (bicyclo)                                                ______________________________________                                          ##STR93##                                                                     R.sup.1          R.sup.2                                                       ______________________________________                                          ##STR94##       CH.sub.3                                                      "                C.sub.2 H.sub.5                                               "                n-C.sub.3 H.sub.7                                             "                i-C.sub.3 H.sub.7                                             "                n-C.sub.4 H.sub.9                                             "                CH.sub.2CHCH.sub.2                                             ##STR95##       i-C.sub.3 H.sub.7                                             "                C.sub.2 H.sub.5                                                ##STR96##       CH.sub.3                                                      "                C.sub.2 H.sub.5                                               "                i-C.sub.3 H.sub.7                                              ##STR97##       C.sub.2 H.sub.5                                               "                i-C.sub.3 H.sub.7                                              ##STR98##       CH.sub.3                                                      "                C.sub.2 H.sub.5                                               "                n-C.sub.3 H.sub.7                                             "                i-C.sub. 3 H.sub.7                                            ______________________________________                                          ##STR99##                                                                     R.sup.1        R.sup.2         Y                                               ______________________________________                                          ##STR100##                                                                                    ##STR101##     H                                                ##STR102##    OCH.sub.3       H                                                ##STR103##    OCH.sub.3       CH.sub.3                                         ##STR104##                                                                                    ##STR105##     H                                                ##STR106##                                                                                    ##STR107##     H                                                ##STR108##                                                                                    ##STR109##     H                                                ##STR110##                                                                                    ##STR111##     H                                                ##STR112##                                                                                    ##STR113##     H                                                ##STR114##                                                                                    ##STR115##     H                                                ##STR116##                                                                                    ##STR117##     H                                               ______________________________________                                    

Sulfurous acid esters of glycolic acid amides, azetidine carbothioates and butynyl carbamates may also be used as components in addition to the active ingredients listed above.

The sulfurous acid esters of glycolic acid amides (a) may be obtained by reacting a glycolic acid amide with an alkyl chlorosulfinate at 10° to 15° C. in an inert solvent and in the presence of an agent capable of binding hydrogen chloride.

For instance, O-ethyl-O-(1-carbonylmethylazacycloheptane)sulfite may be prepared by dripping a solution of 12.9 parts by weight of ethyl chlorosulfinate in 50 parts by weight of benzene at 10° to 15° C. into 15.7 parts by weight of glycolic acid hexamethylene amide dissolved together with 8 parts by weight of pyridine in 50 parts by weight of dry benzene. After 30 minutes the precipitated pyridinium hydrochloride is filtered off and the organic phase washed with water. After drying has been effected, the benzene is distilled off. There is obtained 20.4 parts by weight of the desired product. The compound has the following structure: ##STR118## n₂₅ =1.4910.

The following active ingredients may for example be used:

N-methylacetanilido-(α-ethylsulfite)

N-methylacetanilido-(α-isopropylsulfite)

N-(butyn-1-yl-3)-acetanilido-(α-ethylsulfite)

N-(butyn-1-yl-3)-acetanilido-(α-isopropylsulfite)

N-(butyn-1-yl-3)-acetanilido-(α-methylsulfite) m.p.: 69° to 70° C.

N-isopropylacetanilido-(α-methylsulfite) m.p.: 60° to 61° C.

N-ethylacetanilido-(α-propylsulfite) n₂₅ ^(D) : 1.5295

N-ethylacetanilido-(α-isopropylsulfite) n₂₅ ^(D) : 1.5164

N-ethylacetanilido-(α-methylsulfite) n₂₅ ^(D) : 1.5118

N-ethylacetanilido-(α-ethylsulfite) n₂₅ ^(D) : 1.5010

N-methyl-(4-methoxyacetanilido)-(α-isopropylsulfite)

N-(butyn-1-yl-3)-(4-methoxyacetanilido)-(α-isopropylsulfite)

N-methyl-(p-methylacetanilido)-(α-isopropylsulfite)

N-butyn-1-yl-3)-(p-methylacetanilido)-(α-isopropylsulfite)

N-(2-methylbenzyl)-acetanilido-(α-methylsulfite)

N-(2-methylbenzyl)-acetanilido-(α-ethylsulfite)

N-(2-methylbenzyl)-acetanilido-(α-propylsulfite)

N-(2-methylbenzyl)-acetanilido-(α-isopropylsulfite)

N-tert-butylacetanilido-(α-isopropylsulfite) m.p.: 78° C.

N-tert-butylacetanilido-(α-methylsulfite) m.p.: 57° C.

N-methylacetanilido-(α-sec-butylsulfite), n₂₅ =1.5083

N-(butyn-1-yl-3)-acetanilido-(α-isobutylsulfite) n₂₅ : 1.5098

N-(butyn-1-yl-3)-acetanilido-(α-sec-butylsulfite) n₂₅ : 1.5132

N-(butyn-1-yl-3)-acetanilido-(α-n-butylsulfite) n₂₅ : 1.5172

N-isobutylacetanilido-(α-methylsulfite) n₂₅ : 1.5229

N-isobutylacetanilido-(α-ethylsulfite) n₂₅ : 1.5100

N-methylacetanilido-(α-n-butylsulfite) n₂₅ : 1.5144

N-isobutylacetanilido-(α-propylsulfite) n₂₅ : 1.5059

N-isobutylacetanilido-(α-isopropylsulfite) n₂₅ : 1.5028

N-methylacetanilido-(α-methylsulfite)

N-methylacetanilido-(α-isobutylsulfite)

N-(butyn-1-yl-3)-acetanilido-(α-methylsulfite)

N-methyl-(2-methylacetanilido)-(α-methylsulfite)

N-methyl-(4-methylacetanilido)-(α-methylsulfite)

N-methyl-(4-methoxyacetanilido)-(α-methylsulfite)

N-methyl-(3-chloroacetanilido)-(α-methylsulfite)

N-methyl-(2-methylacetanilido)-(α-ethylsulfite)

N-methylacetanilido-[α-(1-methyl-2-methoxy)-ethylsulfite]

N-methyl-(4-methylacetanilido)-(α-ethylsulfite)

N-methyl-(4-methoxyacetanilido)-(α-ethylsulfite)

N-methyl-(3-chloroacetanilido)-(α-ethylsulfite)

N-methyl-(2-methylacetanilido)-(α-isopropylsulfite)

N-methyl-(3-chloroacetanilido)-(α-isopropylsulfite)

N-methyl-(4-methylacetanilido)-(α-n-butylsulfite)

O-methyl-O-(1-carbonylmethylazacycloheptane)-sulfite; n₂₅ =1.4955

O-isopropyl-O-(1-carbonylmethylazacycloheptane)-sulfite; n₂₅ =1.4695

O-butyl-O-(1-carbonylmethylazacycloheptane)-sulfite; n₂₅ =1.4875

O-propyl-O-(1-carbonylmethylazacycloheptane)-sulfite; n₂₅ =1.4828

O-isopropyl-O-(1-carbonylmethylazacycloheptane)-sulfite; m.p.=58° to 59° C.

O-ethyl-O-(1-carbonylmethyl-2-methylazacycloheptane)-sulfite; n₂₅ =1.4882

O-isopropyl-O-(1-carbonylmethyl-2-methylazacycloheptane)-sulfite; n₂₅ =1.4740

O-methyl-O-(1-carbonylmethyl-2,3-dimethylazacycloheptane)-sulfite; n₂₅ =1.4952

O-ethyl-O-(1-carbonylmethyl-2,3-dimethylazacycloheptane)-sulfite; n₂₅ =1.4860

O-propyl-O-(1-carbonylmethyl-2,3-dimethylazacycloheptane)-sulfite; n₂₅ =1.4849

O-isopropyl-O-(1-carbonylmethyl-2,3-dimethylazacycloheptane)-sulfite; n₂₅ =1.4749

O-ethyl-O-(1-carbonylmethyl-3,5,5-trimethyl-(3,3,5-trimethyl)-azacycloheptane)-sulfite; n₂₅ =1.4850

(1:1 isomer mixture of the 3,3,5- and 3,5,5-trimethyl derivative)

O-isopropyl-O-(1-carbonylmethyl-3-methyl-(2-methyl)-azacycloheptane)-sulfite; n₂₅ =1.4735

(isomer mixture, 55% of which being the 3-methyl and 45% of which the 2-methyl derivative)

O-ethyl-O-(1-carbonylmethylazacycloheptane)-sulfite

O-n-propyl-O-(1-carbonylmethylazacycloheptane)-sulfite

O-methyl-O-(1-carbonylmethyl-3-methylazacycloheptane)-sulfite

O-ethyl-O-(1-carbonylmethyl-3-methylazacycloheptane)-sulfite

O-isopropyl-O-(1-carbonylmethyl-3-methylazacycloheptane)-sulfite

O-ethyl-O-(1-carbonylmethyl-4-methylazacycloheptane)-sulfite

O-isopropyl-O-(1-carbonylmethyl-4-methylazacycloheptane)-sulfite

O-methyl-(1-carbonylmethyl-3-azabicyclo-[3,2,0]-heptane)-sulfite

O-ethyl-(1-carbonylmethyl-3-azabicyclo-[3,2,0]-heptane)-sulfite

O-n-propyl-(1-carbonylmethyl-3-azabicyclo-[3,2,0]-heptane)-sulfite

O-isopropyl-(1-carbonylmethyl-3-azabicyclo-[3,2,0]-heptane)-sulfite

O-isopropyl-O-(1-carbonylmethyl-2-methyl-(3-methyl)-azacycloheptane)-sulfite; n₂₅ =1.4698

(isomer mixture, 75% of which is the 2-methyl and 25% of which the 3-methyl derivative)

O-allyl-O-(1-carbonylmethyl-2,3-dimethylazacycloheptane)-sulfite n₂₅ =1.4970

O-allyl-O-(1-carbonylmethylazacycloheptane)-sulfite; n₂₅ =1.5026

O-(butyn-1-yl-3)-O-(1-carbonylmethyl-2,3-dimethylazacycloheptane)-sulfite; n₂₅ =1.4929

O-(butyn-1-yl-3)-O-(1-carbonylmethyl-3-methylazacycloheptane)-sulfite; n₂₅ =1.4965

O-ethyl-O-(1-carbonylmethylazacyclohexane)-sulfite

O-isopropyl-O-(1-carbonylmethylazacyclohexane)-sulfite

O-methyl-O-(1-carbonylmethyl-2-methylazacyclohexane)-sulfite

O-allyl-O-(1-carbonylmethyl-2-methylazacyclohexane)-sulfite

O-isopropyl-O-(1-carbonylmethyl-2-methylazacyclohexane)-sulfite

O-isopropyl-O-(1-carbonylmethyl-3-methylazacyclohexane)-sulfite

O-(β-chloroethyl)-O-(1-carbonylmethyl-3-methylazacyclohexane)-sulfite

O-ethyl-O-(1-carbonylmethyl-4-methylazacyclohexane)-sulfite

O-allyl-O-(1-carbonylmethyl-4-methylazacyclohexane)-sulfite

O-(β-chloroethyl)-O-(1-carbonylmethyl-4-methylazacyclohexane)-sulfite

O-methyl-O-(1-carbonylmethyl-3,3-dimethylazacyclohexane)-sulfite

O-isopropyl-O-(1-carbonylmethyl-3,3-dimethylazacyclohexane)-sulfite

O-(β-chloroethyl)-O-(1-carbonylmethyl-3,5,5-trimethyl)-(3,3,5-trimethylazacycloheptane)-sulfite

(1:1 isomer mixture of the 3,5,5- and the 3,3,5-trimethyl derivative).

A component may make up from 5 to 95 wt%, preferably 20 to 80 wt%, of an active ingredient composition according to the invention.

The amount used of the agents according to the invention may vary and depends in essence on the type of effect to be achieved; it is generally from 0.1 to 15 (and more), preferably from 0.2 to 6, kg per hectare of active ingredient. The agents according to the invention may be used once or several times before of after planting, before sowing, and before, during or after emergence of the crop plant and unwanted plants.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, (including high-percentage oily or aqueous suspensions) dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

There may be added to the compositions or individual active ingredients (if desired, immediately before use (tankmix)) oils of various types, wetting agents or adherents, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other herbicidally effective compounds such as

substituted anilines

substituted aryloxycarboxylic acids and salts, esters and amides thereof,

substituted ethers

substituted arsonic acids and their salts, esters and amides

substituted benzimidazoles

substituted benzisothiazoles

substituted benzothiadiazinone dioxides

substituted benzoxazines

substituted benzoxazinones

substituted benzothiadiazoles

substituted biurets

substituted quinolines

substituted carbamates

substituted aliphatic carboxylic acids and their salts, esters and amides

substituted aromatic carboxylic acids and their salts, esters and amides

substituted carbamoylalkylthiol- or -dithiophosphates substituted quinazolines

substituted cycloalkylamidocarbothiolic acids and their salts, esters and amides

substituted cycloalkylcarbonamidothiazoles

substituted dicarboxylic acids and their salts, esters and amides

substituted dihydrobenzofuranyl sulfonates

substituted disulfides

substituted dipyridylium salts

substituted dithiocarbamates

substituted dithiophosphoric acids and their salts, esters and amides

substituted ureas

substituted hexahydro-1H-carbothioates

substituted hydantoins

substituted hydrazides

substituted hydrazonium salts

substituted isoxazole pyrimidones

substituted imidazoles

substituted isothiazole pyrimidones

substituted ketones

substituted naphthoquinones

substituted aliphatic nitriles

substituted aromatic nitriles

substituted oxadiazoles

substituted oxadiazinones

substituted oxadiazolidine diones

substituted oxadiazine diones

substituted phenols and their salts and esters

substituted phosphonic acids and their salts, esters and amides

substituted phosphonium chlorides

substituted phosphonalkyl glycines

substituted phosphites

substituted phosphoric acids and their salts, esters and amides

substitutes piperidines

substituted pyrazoles

substituted pyrazole alkylcarboxylic acids and their salts,

esters and amides

substituted pyrazolium salts

substituted pyrazolium alkyl sulfates

substituted pyridazines

substituted pyridazones

substituted pyridine carboxylic acids and their salts, esters and amides

substituted pyridines

substituted pyridine carboxylates

substituted pyridinones

substituted pyrimidines

substituted pyrimidones

substituted pyrrolidine carboxylic acid and its salts, esters and amides

substituted pyrrolidines

substituted pyrrolidones

substituted arylsulfonic acids and their salts, esters and amides

substituted styrenes

substituted tetrahydrooxadiazine diones

substituted tetrahydroxadiazole diones

substituted tetrahydromethanoindenes

substituted tetrahydroxadiazole thiones

substituted tetrahydrothiadiazine thiones

substituted tetrahydrothiadiazole diones

substituted aromatic thiocarbonylamides

substituted thiocarboxylic acids and their salts, esters and amides

substituted thiol carbamates

substituted thioureas

substituted thiophosphoric acids and their salts, esters and amides

substituted triazines

substituted triazoles

substituted uracils, and

substituted uretidine diones.

The last-mentioned herbicidal compounds may also be applied before or after the compositions according to the invention.

These agents may be added to the compositions according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators.

The new compositions have a strong herbicidal action and may therefore be used as weedkillers or for controlling the growth of unwanted plants. Whether the new active ingredients are used as total or selective agents depends in essence on the amount of ingredient used per unit area.

By weeds and unwanted plant growth are meant all monocotyledonous and dicotyledonous plants which grow in loci where they are not desired.

The agents according to the invention may therefore be used for controlling for instance

    ______________________________________                                         Gramineae, such as                                                             Cynodon spp.        Dactylis spp.                                              Digitaria spp.      Avena spp.                                                 Echinochloa spp.    Bromus spp.                                                Setaria spp.        Uniola spp.                                                Panicum spp.        Poa spp.                                                   Alopecurus spp.     Leptochloa spp.                                            Lolium spp.         Brachiaria spp.                                            Sorghum spp.        Eleusine spp.                                              Agropyron spp.      Cenchrus spp.                                              Phalaris spp.       Eragrostis spp.                                            Apera spp.          Phragmites communis                                        etc.;                                                                          Cyperaceae, such as                                                            Carex spp.          Eleccharis spp.                                            Cyperus spp.        Scirpus spp.                                               etc.;                                                                          dicotyledonous weeds, such as                                                  Malvaceae, e.g.                                                                Abutilon theoprasti Hibiscus spp.                                              Sida spp.           Malva spp.                                                 etc.;                                                                          Compositae, such as                                                            Ambrosia spp.       Centaurea spp.                                             Lactuca spp.        Tussilago spp.                                             Senecio spp.        Lapsana communis                                           Sonchus spp.        Tagetes spp.                                               Xanthium spp.       Erigeron spp.                                              Iva spp.            Anthemis spp.                                              Galinsoga spp.      Matricaria spp.                                            Taraxacum spp.      Artemisia spp.                                             Chrysanthemum spp.  Bidens spp.                                                Cirsium spp.        etc.;                                                      Convolvulaceae, such as                                                        Convolvulus spp.    Cuscuta spp.                                               Ipomoea spp.        Jaquemontia tamnifolia                                     etc.;                                                                          Cruciferae, such as                                                            Barbarea vulgaris   Arabidopsis thaliana                                       Brassica spp.       Descurainea spp.                                           Capsella spp.       Draba spp.                                                 Sisvmbrium spp.     Coronopus didymus                                          Thlaspi spp.        Lepidium spp.                                              Sinapis arvensis    Raphanus spp.                                              etc.;                                                                          Geraniaceae, such as                                                           Erodium spp.        Geranium spp.                                              etc.;                                                                          Portulacaceae, such as                                                         Portulaca spp.      etc.;                                                      Primalaceae, such as                                                           Anagallis arvensis  Lysimachia spp.                                            etc.;                                                                          Rubiaceae, such as                                                             Richardia spp.      Diodia spp.                                                Galium spp.         etc.;                                                      Scrophulariacea, such as                                                       Linaria spp.        Digitalis spp.                                             Veronica spp.       etc.;                                                      Solanaceae, such as                                                            Physalis spp.       Nicandra spp.                                              Solanum spp.        Datura spp.                                                etc.;                                                                          Urticaceae, such as                                                            Urtica spp.                                                                    Violaceae, such as                                                             Viola spp.          etc.;                                                      Zygophyllaceae, such as                                                        Tribulus terrestris etc.;                                                      Euphorbiaceae, such as                                                         Mercurialis annua   Euphorbia spp.                                             Umbelliferae, such as                                                          Daucus carota       Ammi majus                                                 Aethusa cynapium    etc.;                                                      Commelinaceae, such as                                                         Commelina spp.      etc.;                                                      Labiatae, such as                                                              Lamium spp.         Galeopsis spp.                                             etc.;                                                                          Leguminosae, such as                                                           Medicago spp.       Sesbania exaltata                                          Trifolium spp.      Cassia spp.                                                Vicia spp.          Lathyrus spp.                                              etc.;                                                                          Plantaginaceae, such as                                                        Plantago spp.       etc.;                                                      Polygonaceae, such as                                                          Polygonum spp.      Fagopyrum spp.                                             Rumex spp.          etc.;                                                      Aizoaceae, such as                                                             Mollugo verticillata                                                                               etc.;                                                      Amaranthaceae, such as                                                         Amaranthus spp.     etc.;                                                      Boraginaceae, such as                                                          Amsinckia spp.      Anchusa spp.                                               Myostis spp.        Lithospermum spp.                                          etc.;                                                                          Caryophyllaceae, such as                                                       Stellaria spp.      Silene spp.                                                Spergula spp.       Cerastium spp.                                             Saponaria spp.      Agrostemma githago                                         Scleranthus annuus  etc.;                                                      Chenopodiaceae, such as                                                        Chenopodium spp.    Atriplex spp.                                              Kochia spp.         Menolepsis nuttalliana                                     Salsola Kali        etc.;                                                      Lythraceae, such as                                                            Cuphea spp.         etc.;                                                      Oxalidaceae, such as                                                           Oxalis spp.                                                                    Ranunculaceae, such as                                                         Ranunculus spp.     Adonis spp.                                                Delphinium spp.     etc.;                                                      Papaveraceae, such as                                                          Papaver spp.        Fumaria offinicalis                                        etc.;                                                                          Onagraceae, such as                                                            Jussiaea spp.       etc.;                                                      Rosaceae, such as                                                              Alchemillia spp.    Potentilla spp.                                            etc.;                                                                          Potamogetonaceae, such as                                                      Potamogeton spp.    etc.;                                                      Najadaceae, such as                                                            Najas spp.          etc.;                                                      Equisetaceae                                                                   Equisetum spp.      etc.;                                                      Marsileaceae, such as                                                          Marsilea quadrifolia                                                                               etc.;                                                      Polypodiaceae,                                                                 Pteridium quilinum                                                             Alismataceae, such as                                                          Alisma spp.         Sagittaria sagittifolia                                    etc.                                                                           The herbicides according to the invention may be employed                      in cereal crops such as                                                        Avena spp.          Sorghum                                                    Triticum spp.       Zea mays                                                   Hordeum spp.        Panicum miliaceum                                          Secale spp.         Oryza spp.                                                 Saccharum offinicarum                                                          and in dicotyledon crops such as                                               Cruciferae, e.g.                                                               Brassica spp.       Raphanus spp.                                              Sinapis spp.        Lepidium spp.                                              Compositae, e.g.                                                               Lactuca spp.        Carthamus spp.                                             Helianthus spp.     Scorzonera spp.                                            Malvaceae, e.g.                                                                Gossypium hirsutum                                                             Leguminosae, e.g.                                                              Medicago spp.       Phaseolus spp.                                             Trifolium spp.      Arachis spp.                                               Pisum spp.          Glycine max.                                               Chenopodiaceae, e.g.                                                           Beta vulgaris                                                                  Spinacia spp.                                                                  Solanaceae, e.g.                                                               Solanum spp.        Capsicum annuum                                            Nicotiania spp.                                                                Linaceae, e.g.                                                                 Linum spp.                                                                     Umbelliferae, e.g.                                                             Petroselinum spp.   Apium graveolens                                           Daucus carota                                                                  Rosaceae, e.g.      Fragaria                                                   Cucurbitaceae, e.g.                                                            Cucumis spp.        Cucurbita spp.                                             Liliaceae, e.g.                                                                Allium spp.                                                                    Vitaceae, e.g.                                                                 Vitis vinifera                                                                 Bromeliaceae, e.g.                                                             Ananas sativus                                                                 ______________________________________                                    

The compositions may also be used as total agents on ditches, aquatic areas, railway track, waste and barren land, etc.

The compositions according to the invention were tested in the greenhouse and in the open. Their action corresponds to that of the compositions employed in the following examples.

EXAMPLE 1

In the greenhouse, various plants were treated at a growth height of from 2 to 16 cm with the following amounts of the following individual active ingredients and compositions thereof as dispersions, emulsions or tankmixes:

I 1-phenyl-4-amino-5-chloropyridazone-(6)

II O-(isopropylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide

III O-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide,

XII 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate

XIII 3-(N-m-trifluoromethylphenylcarbamoyloxy)-(p-methylphenyl)methylcarbamate

XIV 3-(N-m-methylphenylcarbamoyloxy)-acetoacetic acid anilide

XV 4-chlorobutyn-2-yl-1-N-3-chlorophenylcarbamate

XVI methyl α-chloro-β-(4-chlorophenyl)-propionate

XVII 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

each at rates of 0.5, 1, 1.5 and 2 kg/ha;

I+III+XII, I+III+XIII, I+III+XIV,

each at rates of 0.5+0.5+0.5, 1+0.5+0.5, 0.5+1+0.5, and 0.5+0.5+1 kg/ha;

II+XII, II+XIII, II+XIV, II+XV, II+XVI, II+XVII, III+XII, III+XIII, III+XIV, III+XV, III+XVI, III+XVII,

each at rates of 1+0.5, 0.5+1, 0.5+0.5 and 1+1 kg/ha.

After 2 to 3 weeks it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop tolerance.

The results are given below:

    ______________________________________                                         Active ingredient                                                                             I             II                                                kg/ha          0.5   1     1.5 2       0.5 1   1.5 2                           ______________________________________                                         Crop plants:                                                                   Beta vulgaris  0     0     0   0       0   0   0   0                           Unwanted plants:                                                               Avena fatua    5     13    15  25      30  50  55  60                          Echinochloa crus-galli                                                                        15    25    40  53      45  70  78  85                          Matricaria chamomilla                                                                         35    45    50  60      25  45  55  60                          ______________________________________                                         Active ingredient                                                                             III                                                             ______________________________________                                         Beta vulgaris  0     0     0   0                                               Avena fatua    25    50    60  65                                              Echinochloa crus-galli                                                                        45    70    75  80                                              Matricaria chamomilla                                                                         20    40    85  95                                              ______________________________________                                         Active ingredient                                                                             XII           XIII                                              ______________________________________                                         Beta vulgaris  0     0     5   15      0   0   0   0                           Avena fatua    3     20    25  30      10  15  30  40                          Echinochloa crus-galli                                                                        10    15    20  30      15  30  65  80                          Matricaria chamomilla                                                                         15    30    60  80      15  30  50  70                          ______________________________________                                         Active ingredient                                                                             XIV           XV                                                kg/ha          0.5   1     1.5 2       0.5 1   1.5 2                           ______________________________________                                         Beta vulgaris  0     0     0   0       0   0   0   0                           Avena fatua    5     10    15  20      30  60  75  90                          Echinochloa crus-galli                                                                        10    30    50  65      7   12  20  30                          Matricaria chamomilla                                                                         10    25    35  50      5   10  20  25                          ______________________________________                                         Active ingredient                                                                             XVI           XVII                                              ______________________________________                                         Beta vulgaris  0     0     0   0       0   0   5   7                           Avena fatua    30    45    60  75      32  60  80  90                          Echinochloa crus-galli                                                                        0     2     10  14      0   3   5   10                          Matricaria chamomilla                                                                         0     4     10  15      0   9   10  15                          ______________________________________                                         Active ingredient                                                              kg/ha          I + III + XII                                                   ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    75       80       98     95                                     Echinochloa crus-galli                                                                        100      100      100    100                                    Matricaria chamomilla                                                                         100      100      100    100                                    ______________________________________                                         Active ingredient                                                                             I + III + XIII                                                  ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    78       85       100    100                                    Echinochloa crus-galli                                                                        100      100      100    100                                    Matricaria chamomilla                                                                         100      100      100    100                                    ______________________________________                                         Active ingredient                                                                             I + III + XIV                                                   ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    80       85       100    80                                     Echinochloa crus-galli                                                                        100      100      100    100                                    Matricaria chamomilla                                                                         100      100      100    100                                    ______________________________________                                         Active ingredient                                                                            II + XII                                                         kg/ha         1 +  0.5 0.5 + 1  0.5 + 0.5                                                                              1 + 1                                  ______________________________________                                         Beta vulgaris 0        0        0      0                                       Avena fatua   91       88       71     100                                     Echinochloa crus-galli                                                                       100      100      95     100                                     Matricaria chamomilla                                                                        98       96       80     100                                     ______________________________________                                         Active ingredient                                                                             II + XIII                                                       ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    100      100      80     100                                    Echinochloa crus-galli                                                                        100      100      94     100                                    Matricaria chamomilla                                                                         100      96       80     100                                    ______________________________________                                         Active ingredient                                                                             II + XIV                                                        ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    93       80       73     100                                    Echinochloa crus-galli                                                                        100      100      92     100                                    Matricaria chamomilla                                                                         95       90       75     100                                    ______________________________________                                         Active ingredient                                                                             II+ XV                                                          ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    100      100      100    100                                    Echinochloa crus-galli                                                                        100      95       90     100                                    Matricaria chamomilla                                                                         90       72       70     95                                     ______________________________________                                         Active ingredient                                                                             II + XVI                                                        ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    100      100      100    100                                    Echinochloa crus-galli                                                                        100      87       81     100                                    Matricaria chamomilla                                                                         85       68       63     90                                     ______________________________________                                         Active ingredient                                                                            II + XVII                                                        kg/ha         1 + 0.5  0.5 + 1  0.5 + 0.5                                                                              1 + 1                                  ______________________________________                                         Beta vulgaris 0        0        0      0                                       Avena fatua   100      100      100    100                                     Echinochloa crus-galli                                                                       100      88       85     100                                     Matricaria chamomilla                                                                        83       70       63     90                                      ______________________________________                                         Active ingredient                                                                             III + XII                                                       ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    92       85       69     100                                    Echinochloa crus-galli                                                                        100      100      95     100                                    Matricaria chamomilla                                                                         93       90       75     100                                    ______________________________________                                         Active ingredient                                                                             III + XIII                                                      ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    100      95       72     100                                    Echinochloa crus-galli                                                                        100      100      90     100                                    Matricaria chamomilla                                                                         94       90       73     100                                    ______________________________________                                         Active ingredient                                                                             III + XIV                                                       ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    95       75       70     100                                    Echinochloa crus-galli                                                                        100      100      95     100                                    Matricaria chamomilla                                                                         90       86       70     100                                    ______________________________________                                         Active ingredient                                                                            III + XV                                                         kg/ha         1 + 0.5  0.5 + 1  0.5 + 0.5                                                                              1 + 1                                  ______________________________________                                         Beta vulgaris 0        0        0      0                                       Avena fatua   100      100      94     100                                     Echinochloa crus-galli                                                                       100      96       93     100                                     Matricaria chamomilla                                                                        87       80       67     90                                      ______________________________________                                         Active ingredient                                                                            III + XVI                                                        kg/ha         1 + 0.5  0.5 + 1  0.5 + 0.5                                                                              1 + 1                                  ______________________________________                                         Beta vulgaris 0        0        0      0                                       Avena fatua   100      100      95     100                                     Echinochloa crus-galli                                                                       100      86       85     100                                     Matricaria chamomilla                                                                        85       75       60     92                                      ______________________________________                                         Active ingredient                                                                             III + XVII                                                      ______________________________________                                         Beta vulgaris  0        0        0      0                                      Avena fatua    100      100      96     100                                    Echinochloa crus-galli                                                                        100      89       80     100                                    Matricaria chamomilla                                                                         88       80       60     95                                     ______________________________________                                          0 = no damage                                                                  100 = complete destruction                                               

EXAMPLE 2

In the greenhouse, various plants were treated at a growth height of from 2 to 17 cm with the following amounts of the following individual active ingredients and compositions thereof as emulsions or dispersions:

II O-(isopropylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide

1.5, 2, 2.25, 2.5, 3 and 4 kg/ha,

III O-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide

1, 2, 2.5 and 3 kg/ha,

XIII 3-(N-m-trifluoromethylphenylcarbamoyloxy)-(p-methylphenyl)-methylcarbamate

0.5, 0.75, 1, 1.5, 2, 2.5, 3 and 4 kg/ha,

LIV N-methylacetanilido-α-isopropylsulfite

1 and 2 kg/ha,

LXIV O-(dimethylaminosulfonyl)-glycolic acid-N-methylanilide

1 and 2 kg/ha,

LXV O-(dimethylaminosulfonyl)-glycolic acid-N-ethylanilide

1 and 2 kg/ha,

XIII+II 0.5+1.5, 0.5+2.5, 0.75+2.25, 1+1.5, 1+2 and 1.5+2.5 kg/ha,

XIII+III 0.5+2, 1+1 and 1+2 kg/ha,

XIII+LIV 1+1 kg/ha,

XIII+LXIV 1+1 kg/ha,

XIII+LXV 1+1 kg/ha.

After 2 to 3 weeks it was ascertained that the compositions had a better herbicidal action than their components, combined with superior crop plant compatibility.

The results are given below:

    __________________________________________________________________________     Active ingredient                                                                           II              III                                               kg/ha       1.5                                                                              2  2.25                                                                              2.5                                                                               3  4  1 2  2.5                                                                               3                                         __________________________________________________________________________     Crop plants:                                                                   Beta vulgaris                                                                              0 0  0  0  0  10 0 0  0  0                                         Unwanted plants:                                                               Avena fatua 55                                                                               60 60 63 65 70 50                                                                               65 68 70                                        Echinochloa crus-galli                                                                     78                                                                               80 85 90 95 100                                                                               70                                                                               80 85 90                                        Stellaria media                                                                            25                                                                               30 33 34 35 40 15                                                                               30 35 40                                        Galium aparine                                                                             24                                                                               28 30 35 40 46 15                                                                               25 35 41                                        Chenopodium album                                                                          50                                                                               55 56 58 60 70 30                                                                               40 43 45                                        Alopecurus myosuroides                                                                     95                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90                                                                               100                                                                               100                                                                               100                                       Lamium amplexicaule                                                                        30                                                                               40 45 48 50 60 15                                                                               25 30 35                                        __________________________________________________________________________     Active ingredient                                                                          XIII                   LIV LXIV LX                                 kg/ha       0.5                                                                              0.75                                                                              1  1.5                                                                               2  2.5                                                                               3  4  1 2 1 2  1 2                                __________________________________________________________________________     Beta vulgaris                                                                              0 0  0  0  0  15 20 25 0 0 0 0  0 0                                Avena fatua 10                                                                               12 15 30 40 45 50 60 35                                                                               50                                                                               40                                                                               60 45                                                                               70                               Echinochloa crus-galli                                                                     16                                                                               25 35 65 80 85 90 98 50                                                                               80                                                                               65                                                                               80 60                                                                               95                               Stellaria media                                                                            70                                                                               86 95 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               25                                                                               30                                                                               10                                                                               20 20                                                                               30                               Galium aparine                                                                             28                                                                               40 55 60 70 80 90 100                                                                               0 20                                                                               15                                                                               30 10                                                                               30                               Chenopodium album                                                                          60                                                                               85 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               5 30                                                                               25                                                                               50 25                                                                               45                               Alopecurus myosuroides                                                                     5 20 50 55 60 65 70 80 50                                                                               85                                                                               80                                                                               100                                                                               85                                                                               100                              Lamium amplexicaule                                                                        60                                                                               80 90 95 100                                                                               100                                                                               100                                                                               100                                                                               15                                                                               25                                                                               20                                                                               40 25                                                                               35                               __________________________________________________________________________     Active Ingredient                                                                          XIII + II           XIII + III                                                 0.5+                                                                              0.5+                                                                              0.75+      1.5 +                                             kg/ha       1.5                                                                               2.5                                                                               2.25                                                                               1+1.5                                                                              1+2                                                                               2.5                                                                               0.5+2                                                                              1+1                                                                               1+2                                     __________________________________________________________________________     Beta vulgaris                                                                              0  0  0   0   0  5  0   0  0                                       Avena fatua 100                                                                               100                                                                               100 100 100                                                                               100                                                                               100 100                                                                               100                                     Echinochloa crus-galli                                                                     100                                                                               100                                                                               100 100 100                                                                               100                                                                               100 100                                                                               100                                     Stellaria media                                                                            100                                                                               100                                                                               100 100 100                                                                               100                                                                               100 100                                                                               100                                     Galium aparine                                                                             100                                                                               100                                                                               100 100 100                                                                               100                                                                               93  100                                                                               100                                     Chenopodium album                                                                          100                                                                               100                                                                               100 100 100                                                                               100                                                                               100 100                                                                               100                                     Alopecurus myosuroides                                                                     100                                                                               100                                                                               100 100 100                                                                               100                                                                               100 100                                                                               100                                     Lamium amplexicaule                                                                        100                                                                               100                                                                               100 100 100                                                                               100                                                                               100 100                                                                               100                                     __________________________________________________________________________     Active ingredient                                                                          XIII + LIV                                                                            XIII + LXIV                                                                            XIII + LXV                                          kg/ha       1+1    1+1     1+1                                                 __________________________________________________________________________     Beta vulgaris                                                                              0      0       0                                                   Avena fatua 100    95      100                                                 Echinochloa crus-galli                                                                     100    100     100                                                 Stellaria media                                                                            100    100     100                                                 Galium aparine                                                                             95     100     100                                                 Chenopodium album                                                                          100    100     100                                                 Alopecurus myosuroides                                                                     100    100     100                                                 Lamium amplexicaule                                                                        100    100     100                                                 __________________________________________________________________________      0 = no damage                                                                  10 = complete destruction                                                

EXAMPLE 3

In the greenhouse, various plants were treated at a growth height of from 3 to 16 cm with the following amounts of the following individual active ingredients and compositions thereof as dispersions or emulsions:

II O-(isopropylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide

1, 1.5, 2, 2.5, 3, 3.5 and 4 kg/ha,

III O-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide

1, 2, 2.5, 3 and 4 kg/ha,

XIV 3-(N-m-methylphenylcarbamoyloxy)-acetoacetic acid anilide

0.25, 0.5, 1, 2, 2.5, 3 and 4 kg/ha,

XXIV O-(methylaminosulfonyl)-glycolic acid hexamethylene amide,

0.25, 0.5, 1 and 2 kg/ha,

LIV N-methylacetanilido-α-isopropylsulfite

1 and 2 kg/ha,

LXIV O-(dimethylaminosulfonyl)-glycolic acid-N-methylanilide

1, 2, 3 and 4 kg/ha,

LXVI O-(diethylaminosulfonyl)-glycolic acid-N-isopropylanilide

1, 2, 3 and 4 kg/ha,

LXV O-(dimethylaminosulfonyl)-glycolic acid-N-ethylanilide

1 and 2 kg/ha,

XIV+II 0.5+1.5, 0.5+2.5, 0.5+3.5, 1+1, 1+1.5, 1+2 and 1+3 kg/ha,

XIV+III 0.5+2, 1+1, 1+2, 2+1 and 2+2 kg/ha,

XIV+XXIV 0.25+0.25, 0.5+0.5 and 1+1 kg/ha,

XIV+LIV 1+1 kg/ha,

XIV+LXIV 1+1, 2+1 and 2+2 kg/ha,

XIV+LXVI 1+1 kg/ha,

XIV+LXV 1+1 kg/ha.

After 2 to 3 weeks it was ascertained that the compositions had a better herbicidal action than their components, combined with superior crop plant compatibility.

The results are given below:

    __________________________________________________________________________     Active ingredient                                                                          II                 III                                             kg/ha       1 1.5                                                                              2  2.5                                                                               3  3.5                                                                               4  1 2  2.5                                                                               3  4                                    __________________________________________________________________________     Crop plants:                                                                   Beta vulgaris                                                                              0 0 0  0  0  5  10 0 0  0  0  8                                    Unwanted plants:                                                               Avena fatua 50                                                                               55                                                                               60 63 65 68 70 50                                                                               65 68 70 72                                   Echinochloa crus-galli                                                                     70                                                                               78                                                                               80 90 95 100                                                                               100                                                                               70                                                                               80 85 90 100                                  Stellaria media                                                                            15                                                                               25                                                                               30 34 35 37 40 15                                                                               30 35 40 50                                   Galium aparine                                                                             20                                                                               24                                                                               28 35 40 44 46 15                                                                               25 35 41 45                                   Chenopodium album                                                                          40                                                                               50                                                                               55 58 60 65 70 30                                                                               40 43 45 55                                   Alopecurus myosuroides                                                                     90                                                                               95                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               90                                                                               100                                                                               100                                                                               100                                                                               100                                  Lamium amplexicaule                                                                        15                                                                               30                                                                               40 48 50 55 60 15                                                                               25 30 35 40                                   __________________________________________________________________________     Active ingredient                                                                          XIV                XXIV                                            kg/ha       0.25                                                                              0.5                                                                              1 2  2.5                                                                               3  4  0.25                                                                               0.5                                                                             1 2                                        __________________________________________________________________________      Beta vulgaris                                                                             0  0 0 0  0  15 20 0  0 0 5                                        Avena fatua 3  5 10                                                                               20 25 30 40 18 30                                                                               45                                                                               70                                       Echinochloa crus-galli                                                                     5  10                                                                               30                                                                               65 75 80 95 30 40                                                                               70                                                                               90                                       Stellaria media                                                                            30 50                                                                               90                                                                               98 100                                                                               100                                                                               100                                                                               10 20                                                                               40                                                                               60                                       Galium aparine                                                                             20 30                                                                               55                                                                               75 85 95 100                                                                               10 20                                                                               35                                                                               50                                       Chenopodium album                                                                          25 50                                                                               85                                                                               100                                                                               100                                                                               100                                                                               100                                                                               7  15                                                                               25                                                                               45                                       Alopecurus myosuroides                                                                     0  5 25                                                                               40 50 55 70 35 50                                                                               75                                                                               95                                       Lamium amplexicaule                                                                        20 45                                                                               80                                                                               85 95 100                                                                               100                                                                               0  5 20                                                                               45                                       __________________________________________________________________________     Active ingredient                                                                          LIV LXIV       LXVI                                                                               LXV                                             kg/ha       1 2 1 2  3  4  1 2 1 2                                             __________________________________________________________________________     Beta vulgaris                                                                              0 0 0 0  0  15 0 0 0 0                                             Avena fatua 35                                                                               50                                                                               40                                                                               60 70 80 45                                                                               60                                                                               45                                                                               70                                            Echinochloa crus-galli                                                                     50                                                                               80                                                                               65                                                                               80 95 100                                                                               60                                                                               80                                                                               60                                                                               95                                            Stellaria media                                                                            25                                                                               30                                                                               10                                                                               20 30 45 10                                                                               25                                                                               20                                                                               30                                            Galium aparine                                                                             0 20                                                                               15                                                                               30 40 50 20                                                                               40                                                                               10                                                                               30                                            Chenopodium album                                                                          5 30                                                                               25                                                                               50 70 85 40                                                                               55                                                                               25                                                                               45                                            Alopecurus myosuroides                                                                     50                                                                               85                                                                               80                                                                               100                                                                               100                                                                               100                                                                               85                                                                               100                                                                              85                                                                               100                                           Lamium amplexicaule                                                                        15                                                                               25                                                                               20                                                                               40 50 65 20                                                                               40                                                                               25                                                                               35                                            __________________________________________________________________________     Active Ingredient                                                                          XIV + II             XIV + III                                                 0.5+                                                                              0.5+                                                                              0.5+  1+       0.5+                                          kg/ha       1.5                                                                               2.5                                                                               3.5                                                                               1+1                                                                               1.5                                                                               1+2                                                                               1+3                                                                               2  1+1                                                                               1+2                                                                               2+1                                                                               2+2                               __________________________________________________________________________     Beta vulgaris                                                                              0  0  5  0  0  0  15 0  0  0  0  0                                 Avena fatua 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                               Echinochloa crus-galli                                                                     100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                               Stellaria media                                                                            100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                               Galium aparine                                                                             100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                Chenopodium album                                                                         100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                               Alopecurus myosuroides                                                                     100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                               Lamium amplexicaule                                                                        100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                               __________________________________________________________________________     Active Ingredient                                                                          XIV + XXIV                                                                               XIV + LIV                                                                             XIV + LXIV                                                                              XIV + LXVI                                                                             XIV + LXV                                    0.25+                                                                              0.5+                                                           kg/ha       0.25                                                                               0.5                                                                               1+1                                                                               1+1    1+1                                                                               2+1                                                                               2+2                                                                               1+1     1+1                              __________________________________________________________________________     Beta vulgaris                                                                              0   0  0  0      0  0  0  0       0                                Avena fatua 65  75 95 85     90 100                                                                               100                                                                               95      95                               Echinochloa crus-galli                                                                     75  90 100                                                                               100    100                                                                               100                                                                               100                                                                               100     100                              Stellaria media                                                                            80  100                                                                               100                                                                               100    100                                                                               100                                                                               100                                                                               100     100                              Galium aparine                                                                             70  90 100                                                                               95     100                                                                               100                                                                               100                                                                               100     100                              Chenopodium album                                                                          75  100                                                                               100                                                                               100    100                                                                               100                                                                               100                                                                               100     100                              Alopecurus myosuroides                                                                     75  95 100                                                                               100    100                                                                               100                                                                               100                                                                               100     100                              Lamium amplexicaule                                                                        60  50 100                                                                               100    100                                                                               100                                                                               100                                                                               100     100                              __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                               

EXAMPLE 4

In the greenhouse, various plants were treated at a growth height of from 2 to 12 cm with the following amounts of the following individual active ingredients and compositions thereof as emulsions or dispersions:

XII 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate

XIII 3-(N-m-trifluoromethylphenylcarbamoyloxy)-(p-methylphenyl)-methylcarbamate

LXI 3-(N-isopropylaminosulfonyloxyacetyl)-3-azabicyclo-(3,2,2)-nonane

each at rates of 0.5, 1, 1.5, 2 and 3 kg/ha,

XII+LXI and XIII+LXI, each at rates of 2+1, 1+2, 1.5+0.5 0.5+1.5 kg/ha.

After 2 to 3 weeks it was ascertained that, at the lower application rates, the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility. At the higher application rates, the compositions provided good weed control and had good crop tolerance.

The results are given below:

    __________________________________________________________________________                 XII         XIII                                                               0.5                                                                              1 1.5                                                                              2  3  0.5                                                                              1  1.5                                                                               2  3                                           __________________________________________________________________________     Crop plants:                                                                   Beta vulgaris                                                                              0 0 5 15 30 0 0  0  0  20                                          Unwanted plants:                                                               Avena fatua 3 20                                                                               25                                                                               30 40 10                                                                               15 30 40 50                                          Echinochloa crus-galli                                                                     10                                                                               15                                                                               20                                                                               30 40 16                                                                               35 65 80 90                                          Stellaria media                                                                            45                                                                               60                                                                               80                                                                               95 100                                                                               70                                                                               95 100                                                                               100                                                                               100                                         Galium aparine                                                                             15                                                                               30                                                                               50                                                                               70 80 28                                                                               55 60 70 90                                          Chenopodium album                                                                          30                                                                               60                                                                               80                                                                               100                                                                               100                                                                               60                                                                               100                                                                               100                                                                               100                                                                               100                                         Alopecurus myosuroides                                                                     5 10                                                                               15                                                                               20 25 5 50 55 60 70                                          __________________________________________________________________________     Active Ingredients                                                                         LXI        XII + LXI   XIII + LXI                                                               1.5+                                                                              0.5+     1.5+                                                                              0.5+                               kg/ha       0.5                                                                              1 1.5                                                                              2 3  2+1                                                                               1+2                                                                               0.5                                                                               1.5                                                                               2+1                                                                               1+2                                                                               0.5                                                                               1.5                                __________________________________________________________________________     Beta vulgaris                                                                              0 0 0 0 0  15 0  5  0  0  0  0  0                                  Avena fatua 20                                                                               40                                                                               55                                                                               65                                                                               78 100                                                                               100                                                                               85 98 100                                                                               100                                                                               90 100                                Echinochloa crus-galli                                                                     25                                                                               60                                                                               80                                                                               90                                                                               100                                                                               100                                                                               100                                                                               90 100                                                                               100                                                                               100                                                                               100                                                                               100                                Stellaria media                                                                            0 10                                                                               20                                                                               30                                                                               50 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                Galium aparine                                                                             0 5 10                                                                               15                                                                               40 100                                                                               85 90 70 100                                                                               100                                                                               100                                                                               78                                 Chenopodium album                                                                          5 10                                                                               15                                                                               25                                                                               40 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                Alopecurus myosuroides                                                                     50                                                                               80                                                                               90                                                                               95                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                __________________________________________________________________________      0 = no damage                                                                  100 = complete destruction                                                

I claim:
 1. A herbicide composition comprising an inert carrier having dispersed therein a herbicidally effective amount of a mixture of herbicides consisting essentially of(a) O-(isopropylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide, O-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide, O-(methylaminosulfonyl)-glycolic acid hexamethylene amide, N-methylacetanilido-α-isopropylsulfite, O-(dimethylaminosulfonyl)-glycolic acid-N-methylanilide,O-(diethylaminosulfonyl)-glycolic acid-N-isopropylanilide O-(dimethylaminosulfonyl)-glycolic acid-N-methylanilide or 3-(N-isopropylaminosulfonyloxyacetyl)-3-azabicyclo-(3,2,2)-nonane, and (b) 3-methoxycarbonylaminophenyl-N-(3'-methylphenyl)-carbamate, 3-(N-m-trifluoromethylphenylcarbamoyloxy)-(p-methylphenyl)methylcarbamate, or 3-(N-m-methylphenylcarbamoyloxy)-acetoacetic acid anilide in a weight ratio of (a) to (b) in the range of 80:20 to 20:80.
 2. A herbicide composition as claimed in claim 1, wherein compound (a) isO-(isopropylaminosulfonyl)-glycolic acid-N-butyn-1-yl-3-anilide or O-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide and said weight ratio is in the range of 2:1 to 1:2.
 3. A herbicide composition as claimed in claim 1, wherein compound (a) is 3-(N-isopropylaminosulfonyloxyacetyl)-3-azabicyclo-(3,2,2)-nonane,and said weight ratio is in the range of 3:1 to 1:3.
 4. A herbicide composition as claimed in claim 1, wherein compound (a) is O-(methylaminosulfonyl)-glycolic acid hexamethylene amide, and said weight ratio is 1:1. 